Copolymers of starch and cellulose

ABSTRACT

Copolymers comprising cellulose and starch connected by at least one cross-linker, methods of producing the copolymers, and formed articles comprising the copolymers are described herein. The copolymers may be biodegradable and may have improved physical properties when compared to the homopolymers and other biodegradable polymers. In some embodiments, the copolymer may be more flexible than unmodified cellulose may have better structural integrity than unmodified starch.

CLAIM OF PRIORITY

This application is a U.S. national stage filing under 35 U.S.C. §371 ofInternational Application No. PCT/US2012/063643 filed Nov. 6, 2012entitled “COPOLYMERS OF STARCH AND CELLULOSE” which is incorporatedherein by reference.

BACKGROUND

Approximately 140 million tons of petroleum-based polymers are producedannually, and after their initial use, large portions of these areintroduced into the natural ecosystem as waste products. Novelbioplastics incorporating starch, polylactic acid, polyhydroxybutyrate,cellulose, and various copolymers make up about 300,000 tons of thetotal polymer production, and their production is growing at a rate of20% per year. These composite polymers need to be high in molecularweight to provide strength, substituted to confer flexibility,moderately crystalline to impart moisture and vapor pressure resistanceand with engineered points of inflection including intermolecularester-etherification regions to initiate biodegradation. The naturaldegradation process of these polymers requires moisture, humidity,temperature and microbial action to facilitate the degradation.Currently, the functionality of these bioplastics suffers from highwater absorption, brittleness, deformation during processing, and shelflife with environmental factors, such as UV radiation and relativehumidity, increasing the rate of instability associated with thematerial being packaged.

SUMMARY

In some embodiments, copolymers may include cellulose and starchconnected by at least one cross-linker. In some embodiments, thecopolymer may be biodegradable. In some embodiments, the copolymer maybe able to be extruded, sheeted, pressed, laminated, blow-molded, or acombination thereof. In some embodiments, the copolymer may furtherinclude at least one substituent selected from propylene oxide, acetate,maleic, carboxymethyl cellulose, pectin, glycerol, and combinationsthereof.

In certain embodiments, methods of preparing a copolymer may includeproviding a starch and a cellulose; combining the cellulose and thestarch; providing a crosslinking agent; and contacting the combinedcellulose and starch with the crosslinking agent to produce thecopolymer. In some embodiments, a method may further include providing asubstitution agent; and contacting the combined cellulose and starchwith the substitution agent.

In further embodiments, formed articles may comprise any of thecopolymers described herein. In some embodiments, a formed article maybe produced by extruding, sheeting, pressing, laminating, thermoforming,injecting, and/or blow-molding the copolymer.

In still further embodiments, methods of making a biodegradable,water-proof laminate are described. In certain embodiments, a method mayinclude forming a biodegradable copolymer composed of cellulose andstarch, wherein the cellulose and the starch are connected by at leastone cross-linker, and extruding the biodegradable copolymer into alaminate film.

In other embodiments, methods of making a biodegradable liquidpaperboard are described. In certain embodiments, a method may includeheating wood chips in a solution having water and a solute to form apulp, contacting the pulp with a copolymer composed of cellulose andstarch, wherein the cellulose and the starch are connected by at leastone cross-linker, removing at least a portion of water from the pulp toform a moist pulp, and rolling the moist pulp over heated cylinders toform a dry paperboard. In some embodiments, the solute may be, forexample, sodium sulphate, sodium sulphite, potassium sulphite, calciumsulphite, magnesium sulphite, ammonium sulphite, sodium hydroxide,calcium hydroxide, sodium carbonate, calcium oxide, or combinationsthereof.

DETAILED DESCRIPTION

Described herein are copolymers including cellulose and starch connectedby at least one cross-linker, compositions including these copolymers,methods of producing the copolymers and compositions used in thesemethods, and articles of manufacture including the copolymers.Particular embodiments are directed to methods of making biodegradable,water-proof laminate from the copolymers described herein and methods ofmaking biodegradable liquid paperboard. The copolymers are, generally,biodegradable and exhibit improved physical properties when compared tocellulose and starch homopolymers and other biodegradable polymers.

Various embodiments include a copolymer of cellulose and starchconnected by at least one cross-linker, and in some embodiments, thecopolymer may further include at least one substituent selected frompropylene oxide, acetate, maleic, carboxymethyl cellulose, pectin,glycerol, and combinations thereof. Such copolymers are generallybiodegradable, and in some embodiments, these copolymers may be able tobe extruded, sheeted, pressed, laminated, blow-molded, or a combinationthereof. Thus, certain embodiments are directed to extruded, sheeted,pressed, laminated, or blow-molded copolymers and other forms orarticles including these copolymers.

The starch component may be from any source including, for example,corn, potatoes, wheat, or a combination thereof. In some embodiments,the starch may comprise a starch that has been jet cooked, acid washed,homogenized, enzyme treated, sonicated, or a combination thereof.Therefore, the starch component may include fragmented, partiallyfragments, denatured, or partially denatured starches. In someembodiments, the starch may be a high amylose starch. For example, thestarch may have an amylose content of about 50% to about 80%, about 55%to about 75%, about 60% to about 70% or any range or individual valueencompassed by these exemplary ranges. More specific exemplary,non-limiting, starches include those having an amylose content of about50%, about 55%, about 60%, about 62%, about 64%, about 66%, about 68%,about 70%, about 72%, about 74%, about 76%, about 78%, about 80% and anyamount or range of amounts between those listed, inclusive of endpoints.

The amount of starch in the copolymers described herein can vary amongembodiments, and starch will, generally, make up the major constituentof the copolymer. For example, in some embodiments, the copolymer mayhave a starch content of about 60 weight percent (wt. %) to about 98 wt.%, about 70 wt. % to about 95 wt. %, about 80 wt. % to about 90 wt. % orany range or individual value encompassed by these exemplary ranges. Inparticular embodiments, the copolymers may have a starch content ofabout 60 wt. %, about 65 wt. %, about 70 wt. %, about 75 wt. %, about 80wt. %, about 82 wt. %, about 84 wt. %, about 86 wt. %, about 88 wt. %,about 90 wt. %, about 92 wt. %, about 95 wt. %, about 98 wt. %, or anyamount or range of amounts between those listed, inclusive of endpoints.

The cellulose used in the copolymers described herein may be from anysource. For example, in some embodiments, the cellulose may be fromsoftwood, hardwood, recycled paper, rice hulls, sugar cane, sugar beet,wheat or corn husks, bamboo, coconut, cocoa bean hulls, and the like orcombinations thereof. In some embodiments, the cellulose may be treatedto remove at least a portion of hemicellulose, lignin, sugar, phenoliccompounds (including those derived from, but not limited to, benzoicacid and cinnamic acids), poly phenyl oxidase, and the like orcombinations thereof. Thus, the cellulose of some embodiments may have areduced amount when compared to naturally occurring cellulose from theidentified sources or none of these components. In some embodiments, theamount or composition of hemicellulose, lignin, sugar, or phenoliccompounds present in the cellulose may be dependent on the source of thecellulose. In some embodiments, the cellulose may include a cellulosewhich may be alkali treated, acid washed, homogenized, sonicated, or acombination thereof. Therefore, copolymers including fragmented ordenatured or partially fragmented or denatured cellulose are encompassedby embodiments. In some embodiments, the cellulose may include at leastone substituent such as, but not limited to, treatment by sulphites,sodium hydroxide, peroxides, propylene oxide, phosphorous oxychloride,acetate, maleic, nitrate, sodium octenyl or aluminum succinate,chloride, epichlorohydrin hydroxypropyl reaction or phosphorylation byphosphoric anhydrides, mixed phosphate esters including sodiumtripolypolyphosphates or sodium trimetaphosphate. Without wishing to bebound by theory, substituted cellulose may improve flexibility of thecopolymer by providing steric interference and reducing the linearity.

Various crosslinkers may be included in the copolymers described herein.For example, in some embodiments, the at least one cross-linker caninclude di-acyl radicals having optionally substituted C₂ to C₁₀hydrocarbon chains. In particular embodiments, the at least onecross-linker may be malonyl, succinyl, maleyl, glutaryl, adipyl, and thelike and combinations thereof.

The copolymers described above generally exhibit a good combination ofphysical properties while providing a biodegradable material. Forexample, in some embodiments, the copolymer may have better structuralintegrity than the structural integrity of unmodified starch. In someembodiments, the crosslinker may improve the structural integrity of thecopolymer by joining the inversely paired α-1,4 glucose linkages instarch and β-1,4 glucose linkages in cellulose.

Further embodiments include methods for preparing a copolymer mayincluding providing a starch and a cellulose; combining the celluloseand the starch; providing a crosslinking agent; and contacting thecombined cellulose and starch with the crosslinking agent to produce acopolymer. In some embodiments, the method may further include providinga substitution agent such as, for example, propylene oxide, acetate,carboxymethyl cellulose, pectin, glycerol, and the like and combinationsthereof; and contacting the combined cellulose and starch with thesubstitution agent.

The ratio of cellulose to starch in the mixture may vary. For example,in some embodiments, the cellulose and the starch weight ratio may beabout 1:1, about 1:2, about 1:3, about 1:4, about 1:5, about 1:6, about1:7, about 1:8, about 1:9, about 1:10, about 1:11, about 1:12, about1:13, about 1:14, about 1;15, about 1:16, about 1:17, about 1:18, about1:19, about 1:20, or any ratio or range of ratios between those listed,inclusive of endpoints.

In some embodiments, the method may include washing the mixture at lowpH such as, for example, about pH 1 to about pH 4, about pH 1, about pH2, about pH 3, about pH 4, or any pH or pH range between those listed,inclusive of endpoints, to remove phenolics. In still other embodiments,the method may include swelling the cellulose and starch at a high pHsuch as, for example, about pH 7 to about pH 11, about pH 7, about pH 8,about pH 9, about pH 10, about pH 11, or any pH or pH range betweenthose listed, inclusive of endpoints to effect the chemicalsubstitution) after washing at low pH, and still further embodiments caninclude reducing the pH to within an acidic range such as, for example,about pH 3 to about pH 6.9, about pH 3, about pH 4, about pH 5, about pH6, about pH 6.9, or any pH or pH range between those listed, inclusiveof endpoints, after swelling to effectuate a partial crystallization ofthe copolymer. Without wishing to be bound by theory, the additionalsteps of washing, swelling, and reducing the pH may strength thestructure of the copolymer. In other embodiments, a similar affect canbe achieved by reacting the mixture in a counter current reactor suchas, for example, a D-Tank having an Archimedes screw and a gradient pHsolution starting at about pH 3 and moving to about pH 9 and then backto about pH 4 to about pH 6.

The step of contacting the combined cellulose and starch with thecrosslinking agent may occur for any period of time necessary to achievesufficient crosslinking for good structural integrity. For example,crosslinking may be carried out for about 0.5 hours to about 5 hours,about 1 hour to about 4 hours, about 2 hours to about 3 hours, or about0.5 hours, about 1 hour, about 2 hours, about 3 hours, about 4 hours,about 5 hours, or any time or range of time between those listed.Contacting the combined cellulose and starch with the crosslinking agentcan be carried out at room temperature, or the mixture of cellulose,starch and crosslinking agent may be heated. Thus, some embodimentsinclude the step heating a mixture of cellulose, starch and crosslinkingagent. For example, in some embodiments, this contacting may be carriedout at about 20° C. to about 60° C., about 20° C., about 30° C., about40° C., about 50° C., about 60° C., or any temperature or range oftemperatures between those listed, inclusive of endpoints. While ambienttemperatures may be sufficient, minor elevations in chemical reactiontemperatures may increase the rate of reaction.

Some methods can include steps for processing starch before providingthe starch. For example, in some embodiments, processing starch mayinclude heating a high amylose starch and washing the heated starch withan acid such as, for example, phosphoric acid, acetic acid, hydrochloricacid, maleic acid, citric acid, and the like and combinations thereof.Heating the high amylose starch can be carried out by any meansincluding, for example, jet cooking. In some embodiments, processing thestarch may further include homogenizing the washed starch, and incertain embodiments, homogenizing can be carried out at a pressure ofabout 6,000 psi, about 7,000 psi, about 8,000 psi, about 9,000 psi,about 10,000 psi, or any pressure or range of pressures between thoselisted, inclusive of endpoints. In other embodiments, processing thestarch may include sonicating the washed starch at a frequency of, forexample, about 60 kHz, about 100 kHz, about 200 kHz, about 300 kHz,about 400 kHz, about 500 kHz, about 600 kHz, about 700 kHz, about 800kHz, about 900 kHz, about 1,000 kHz, or any frequency or range offrequencies between those listed, inclusive of endpoints.

Some methods can also include processing the cellulose before providingcellulose. For example, in some embodiments include the step of treatingthe cellulose to remove hemicellulose, lignin, sugar, poly phenyloxidase, and the like or a combination thereof. Such methods may furtherinclude contacting the treated cellulose with an alkali such as, forexample, sodium hydroxide, potassium hydroxide, and the like and washingthe alkali-contacted cellulose with an acid such as, for example,phosphoric acid, phosphinic acid, phosphonic acid, acetic anhydride,acetic acid, and the like. Treating can be carried out by any means. Forexample, treating can be carried out by a two-staged milling and washingprocess. In some embodiments, processing cellulose may further includehomogenizing the cellulose, and in some embodiments, the homogenizingcan be carried out at a pressure of about 6,000 psi, about 7,000 psi,about 8,000 psi, about 9,000 psi, about 10,000 psi, or any pressure orrange of pressures between those listed, inclusive of endpoints. Inother embodiments, processing the cellulose may further includesonicating the cellulose a frequency of, for example, about 60 kHz,about 100 kHz, about 200 kHz, about 300 kHz, about 400 kHz, about 500kHz, about 600 kHz, about 700 kHz, about 800 kHz, about 900 kHz, about1,000 kHz, or any frequency or range of frequencies between thoselisted, inclusive of endpoints.

Some methods further include preparing a crosslinking agent. Forexample, a crosslinking agent can be prepared by contacting a di-acidwith acetic anhydride. The di-acid may be a di-acid that includes asubstituted or unsubstituted C₂ to C₁₀ hydrocarbon, and in someembodiments, the di-acid may be malonic acid, succinic acid, maleicacid, glutaric acid, adipic acid, and the like and combinations thereof.

Any of the copolymers described herein can be formed into an article orother useful object such as, for example, food trays, pallets, packagingtrays, bottles, foils, papers, boards, eating utensil or food plates,packing spacers, bottle caps, various containers, banners, microwavablecontainers and packaging, signs, posters, loose fill for packaging,sheets, or cases for thermoforming or injection molding. Thus, incertain embodiments, methods may include the step of forming thecopolymer by methods such as extruding, sheeting, pressing, laminating,thermoforming, injecting, blow-molding, and the like and combinationsthereof. In some embodiments, the formed article may be.

The copolymers described herein may be used for any purpose. In certainembodiments, the copolymers may be used for making biodegradable,water-proof laminates. In some embodiments, a method for making abiodegradable, water-proof laminate may include forming a biodegradablecopolymer of cellulose and starch such as those described above, andextruding the biodegradable copolymer into a laminate film. In someembodiments, the starch may constitute about 80 wt. %, about 82 wt. %,about 84 wt. %, about 86 wt. %, about 88 wt. %, about 90 wt. %, or anyvalue between any two of these values, of the copolymer. In someembodiments, the starch may be a high amylose starch.

In particular embodiments, the extruding step is carried out using atwin-screw extruder having about 5 to about 7 temperature zones that canrange in the temperature zones may vary from about 65° C. to about 125°C. The temperature in successive temperature zones may increasemonotonously in some embodiments, and in certain embodiments, thetemperature in successive temperature zones may initially increase to apeak value and then decrease for the later zones. For example, inembodiments with 5 temperature zones, the temperature of the first zonemay be about 65° C., the temperature of the second zone may be about 75°C., the third zone may have a temperature of about 90° C., the fourthzone may have a temperature of about 125° C., and the fifth zone mayhave a temperature of about 95° C. In embodiments with 7 temperaturezones, the first temperature zone may be at about 65° C., the secondzone may be at about 80° C., the third may be at about 95° C., thefourth may be at about 110° C., the fifth may be at about 125° C., thesixth at about 110° C., and the seventh at about 95° C. Variouspermutations of temperature zones are possible for various embodiments.In some embodiments, the temperature between two successive temperaturezones may differ by about 5° C., about 10° C., about 15° C., about 20°C., about 25° C., about 30° C., about 35° C., about 40° C., about 50°C., about 55° C., about 60° C., or any value between any two of thesevalues.

In various embodiments, the twin-screw pressure may be varied. In someembodiments, the pressure may be about 20 Bar, about 25 Bar, about 30Bar, about 35 Bar, about 40 Bar, or any value between any two of thesevalues. The rotation of the twin-screw determines the speed at which alaminate film is extruded. In some embodiments, the screws may berotated at about 50 rotations per minute (rpm), about 55 rpm, about 60rpm, about 65 rpm, about 70 rpm, or any value between any two of thesevalues, resulting in an extrusion speed of about 0.125 meters/minute(m/min), about 0.12 m/min, about 0.115 m/min, about 0.10 m/min, or anyvalue between any two of these values.

Embodiments are additionally directed to methods of making biodegradableliquid paperboard. A method for making biodegradable liquid paperboardmay include heating wood chips in a solution to form a pulp, contactingthe pulp with a copolymer including cellulose and starch that areconnected by at least one cross-linker, removing at least a portion ofwater from the pulp to form a moist pulp, and rolling the moist pulpover heated cylinders to form a dry liquid paperboard.

In some embodiments, the solution to form a pulp may include salts suchas, for example, sodium sulphate, sodium sulphite, sodium sulphide,sodium metabisulphite, potassium sulphite, calcium sulphite, magnesiumsulphite, sodium hypochlorite, calcium hypochlorite, hypochlorous acid,peracetic acid, persulphate, permanganate, ammonium sulphite, sodiumhydroxide, calcium hydroxide, sodium carbonate, calcium oxide, sodiumchloride, calcium chloride, hydrogen peroxide, and chlorine dioxide. Invarious embodiments, the salts may be used for controlling the hydrationand rate of substitution reaction. Typical concentration of salts usedmay be about 0.5% to about 5% by weight depending on the conditions andthe particular salt being used. In some embodiments, the solution may betreated at room temperature, and in certain embodiments, the solutionmay be heated to a temperature of about 50° C. In embodiments where thesolution has an alkaline pH (from about 9 to about 11) the solution maybe heated to a temperature of about 80° C. to about 120° C. In variousembodiments, it may be desirable for the solution to have reducedmoisture (less than about 20%) so as to allow expansion of the starch.In such embodiments, the moist pulp may be heated to a temperature ofabout 80° C. to about 120° C. In various embodiments, solution may beheated for about 1 hour to about 4 hours under atmospheric pressure.

In some embodiments, the method may further include disposing a layer ofbiodegradable, water-proof laminate on the dry liquid paperboard, and incertain embodiments, the biodegradable, water-proof laminate may includebiodegradable copolymer of cellulose and starch connected by at leastone cross-linker such as those copolymers described above. Variousembodiments further include laminates having multiple layers of thebiodegradable liquid paperboard and the biodegradable, water-prooflaminate. In some embodiments, the layers may be alternately stackedsuch that a laminate layer separates two successive paperboard layers,and in particular embodiments, the top and the bottom layers may be madefrom the laminate. For example, for a multi-layer laminate having 5layers, the first layer may a laminate, the second may be a paperboard,the third may be a laminate, the fourth may be a paperboard, and thefifth may be a laminate layer. Various other permutations may beconfigured using the paperboard and the laminate layers. Such layeredpaperboard-laminate sheets may be used for any suitable purpose known inthe art, such as, for example, for making storage containers for dairyand dairy products, beverages, and the like, for making food trays,plates, and the like, for making food storage containers, for makingpackaging trays for transporting food, fruits, meats, and the like, andso forth.

EXAMPLES Example 1: Cellulose Preparation

Cellulose is introduced to a two staged size reduction milling andwashing process to remove hemicellulose, color, sugar and poly phenoloxidase (PPO). The cellulose is then treated with alkali followed byacid washing in a solution of increasing concentration of acidulants.The alkali treatment is done by either counter current extraction or vatprocessing. The cellulose may then be jet-cooked and/or ultrasonicatedat about 60 kHz to about 1000 kHz to produce micro fibrils for chemicalmodification. The creation of these micro fibular arrays provides asubstrate of exposed high molecular weight polymers which can besubstituted (>5%) and crosslinked (<0.6%).

Example 2: High Amylose Starch Preparation

High amylose polymers derived from starch granules are jet cooked. Thehigh amylose starch is processed by ultrasonication at about 60 kHz toabout 1000 kHz.

Example 3: Copolymer Preparation

The cellulose from Example 1 and the starch from Example 2 are combined(4:1 weight ratio) in a 20% aqueous solution (Dry Solids Basis) using ahigh speed, low air incorporation agitation system (Scott Turbines), attemperatures between 25° C. and 40° C. for a period of up to 2 hours,and then substituted by acetylation, esterification, propylation, orsuccination. The cellulose and the starch are then crosslinked uponaddition of maleic or phosphoric acid derivatives as a crosslinker.Swelling is controlled by salt addition in a gradient alkali to acid pHreaction, the ratio of starch to fiber in solution and the inclusion ofsalt and addition of antimicrobial fractionated oils or sulphides.

The micro fibrils may also be reacted with HA starch and dried to createa new raw material which may be extruded, sheeted and pressed orlaminated into thermoformed trays, bottles, crates or utensils. Thepreparation of these copolymer materials may provide additionalstructural strength with greater tolerance to moisture and gas transfercompared to traditional bioplastic materials.

Example 4: Formed Articles Using Copolymers

A copolymer of Example 3 is injection molded to form a microwavablecontainer. A bottle is separately blow molded using another copolymer ofExample 3.

Example 5: Biodegradable Laminate Preparation

The copolymer of Example 3 is produced and extruded as a film. The filmis prepared using a twin-screw extruder, using 5 zones of temperature(65° C.-80° C.-110° C.-125° C.-95° C.) and a moderate shear screwconfiguration with reverse flights at a pressure of about 30 Bar andscrew speed of about 60 rpm such that the exit rate for the film isabout 0.1 meters per minute.

Example 6: Biodegradable Liquid Paperboard Preparation

The copolymer is prepared in situ with exposed wood chips during a Kraftpaper making process where the jet cooking and sonication step of thesepolymers are performed and the reaction chemicals are added to the pulpmix with the exposed polymers and allowed to react.

The present disclosure is not to be limited in terms of the particularembodiments described in this application, which are intended asillustrations of various aspects. Many modifications and variations canbe made without departing from its spirit and scope, as will be apparentto those skilled in the art. Functionally equivalent methods andapparatuses within the scope of the disclosure, in addition to thoseenumerated herein, will be apparent to those skilled in the art from theforegoing descriptions. Such modifications and variations are intendedto fall within the scope of the appended claims. The present disclosureis to be limited only by the terms of the appended claims, along withthe full scope of equivalents to which such claims are entitled. It isto be understood that this disclosure is not limited to particularmethods, reagents, compounds, compositions or biological systems, whichcan, of course, vary. It is also to be understood that the terminologyused herein is for the purpose of describing particular embodimentsonly, and is not intended to be limiting.

With respect to the use of substantially any plural and/or singularterms herein, those having skill in the art can translate from theplural to the singular and/or from the singular to the plural as isappropriate to the context and/or application. The varioussingular/plural permutations may be expressly set forth herein for sakeof clarity.

It will be understood by those within the art that, in general, termsused herein, and especially in the appended claims (e.g., bodies of theappended claims) are generally intended as “open” terms (e.g., the term“including” should be interpreted as “including but not limited to,” theterm “having” should be interpreted as “having at least,” the term“includes” should be interpreted as “includes but is not limited to,”etc.). It will be further understood by those within the art that if aspecific number of an introduced claim recitation is intended, such anintent will be explicitly recited in the claim, and in the absence ofsuch recitation, no such intent is present. For example, as an aid tounderstanding, the following appended claims may contain usage of theintroductory phrases “at least one” and “one or more” to introduce claimrecitations. However, the use of such phrases should not be construed toimply that the introduction of a claim recitation by the indefinitearticles “a” or “an” limits any particular claim containing suchintroduced claim recitation to embodiments containing only one suchrecitation, even when the same claim includes the introductory phrases“one or more” or “at least one” and indefinite articles such as “a” or“an” (e.g., “a” and/or “an” should be interpreted to mean “at least one”or “one or more”); the same holds true for the use of definite articlesused to introduce claim recitations. In addition, even if a specificnumber of an introduced claim recitation is explicitly recited, thoseskilled in the art will recognize that such recitation should beinterpreted to mean at least the recited number (e.g., the barerecitation of “two recitations,” without other modifiers, means at leasttwo recitations, or two or more recitations). Furthermore, in thoseinstances where a convention analogous to “at least one of A, B, and C,etc.” is used, in general, such a construction is intended in the senseone having skill in the art would understand the convention (e.g., “asystem having at least one of A, B, and C” would include but not belimited to systems that have A alone, B alone, C alone, A and Btogether, A and C together, B and C together, and/or A, B, and Ctogether, etc.). It will be further understood by those within the artthat virtually any disjunctive word and/or phrase presenting two or morealternative terms, whether in the description, claims, or figure, shouldbe understood to contemplate the possibilities of including one of theterms, either of the terms, or both terms. For example, the phrase “A orB” will be understood to include the possibilities of “A” or “B” or “Aand B.”

In addition, where features or aspects of the disclosure are describedin terms of Markush groups, those skilled in the art will recognize thatthe disclosure is also thereby described in terms of any individualmember or subgroup of members of the Markush group.

As will be understood by one skilled in the art, for any and allpurposes, such as in terms of providing a written description, allranges disclosed herein also encompass any and all possible subrangesand combinations of subranges thereof. Any listed range can be easilyrecognized as sufficiently describing and enabling the same range beingbroken down into at least equal halves, thirds, quarters, fifths,tenths, etc. As a non-limiting example, each range discussed herein canbe readily broken down into a lower third, middle third and upper third,etc. As will also be understood by one skilled in the art all languagesuch as “up to,” “at least,” and the like include the number recited andrefer to ranges which can be subsequently broken down into subranges asdiscussed above. Finally, as will be understood by one skilled in theart, a range includes each individual member. Thus, for example, a grouphaving 1-3 substituents refers to groups having 1, 2, or 3 substituents.Similarly, a group having 1-5 substituents refers to groups having 1, 2,3, 4, or 5 substituents, and so forth.

While various compositions, methods, and devices are described in termsof “comprising” various components or steps (interpreted as meaning“including, but not limited to”), the compositions, methods, and devicescan also “consist essentially of” or “consist of” the various componentsand steps, and such terminology should be interpreted as definingessentially closed-member groups.

What is claimed is:
 1. A copolymer comprising cellulose and starch,wherein the cellulose and the starch are connected by at least onecross-linker, and wherein the starch has an amylose content of about 50percent to about 80 percent, and wherein the starch is present at about80 to about 90 weight percent of the copolymer.
 2. The copolymer ofclaim 1, wherein the starch comprises a starch which has been jetcooked, acid washed, homogenized, sonicated, or a combination thereof,and wherein the starch is sourced from corn, potatoes, wheat, or acombination thereof.
 3. The copolymer of claim 1, wherein the cellulosehas been treated to remove at least a portion of hemicellulose, lignin,sugar, phenolic compounds, poly phenyl oxidase, or a combination thereoffrom the cellulose.
 4. The copolymer of claim 1, wherein the cellulosecomprises a cellulose which has been alkali treated, acid washed,homogenized, sonicated, or a combination thereof.
 5. The copolymer ofclaim 1, wherein the cellulose is from a source selected from the groupconsisting of softwood, hardwood, recycled paper, rice hulls, sugarcane, sugar beet, bamboo, and combinations thereof.
 6. The copolymer ofclaim 1, wherein the at least one cross-linker is a di-acyl radicalcomprising a substituted C₂ to C₁₀ hydrocarbon chain or an unsubstitutedC₂ to C₁₀ hydrocarbon chain.
 7. The copolymer of claim 1, furthercomprising at least one substituent selected from the group consistingof propylene oxide, acetate, carboxymethyl cellulose, pectin, glycerol,and combinations thereof.
 8. An article comprising the copolymeraccording to claim
 1. 9. The article of claim 8, wherein the article isa food tray, a pallet, a packaging tray, a bottle, a foil, a paper, aboard, a utensil or plate, a packing spacer, a bottle cap, a container,a banner, a microwavable container, a sign, loose fill for packaging, asheet for thermoforming, a case for thermoforming, or a case forinjection molding.